Zinc hexacyanoferrate (ZnHCF) which is a dimorphic (cubic or rhombohedral) Prussian blue analogue and can be intercalated by both monovalent and divalent ions,is a promising cathode material for rechargeable aqueous metal-ion batteries.In this paper, a simple co-precipitation method is developed to tune the particle morphology of ZnHCF by adjusting the dropping speed at room temperature. Three polyhedral ZnHCF particles, with cubooctahedral, truncated octahedral or octahedral shapes, are obtained at room temperature. Structural transformation from cubic phase of as-prepared ZnHCF to rhombohedral phase is observed by further dehydration of the sample at 70 °C, whereas the dehydrated ZnHCF crystals still hold the identical polyhedral shape as that of the cubic phase particles. Then the influence of shape and facets on electrochemical performance is studied for polyhedral ZnHCF with rhombohedral structure (RZnHCF). RZnHCF sample with cubooctahedral shape possesses the best rate capability and cyclic stability comparing with RZnHCF particles having truncated octahedral or octahedral shapes. Furthermore, the structure of cuboctahedron RZnHCF particles during electrochemical cycling has been monitored with ex situ X-ray diffraction to demonstrate the reversible zinc-ion intercalation mechanism.